Fluorescent Glass Ceramics And Glasses With Europium Content

ABSTRACT

The invention relates to glass ceramics and glasses with a europium content, containing the following components: 
     
       
         
               
               
               
             
                   
                   
               
                   
                 Component 
                 wt.-% 
               
                   
                   
               
                   
                 SiO 2   
                 30.0 to 75.0 
               
                   
                 Al 2 O 3   
                 10.0 to 45.0 
               
                   
                 Europium, calculated as Eu 2 O 3   
                 0.05 to 5.0 
               
                   
                   
               
           
              
              
              
             
             
              
              
              
              
             
          
         
       
     
     and which are suitable in particular for the production of dental restorations, the fluorescence properties of which largely correspond to those of natural teeth.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of and claims priority to U.S. patent application Ser. No. 16/784,824 filed on Feb. 7, 2020, which claims priority to European patent application No. 19157306.2 filed on Feb. 14, 2019, the disclosures of which are incorporated herein by reference in their entirety.

FIELD OF INVENTION

The present invention relates to glass ceramics and glasses which contain europium and are suitable in particular for the production of dental restorations, the fluorescence properties of which largely correspond to those of natural teeth. The invention also relates to a process for the preparation of the glass ceramics and glasses according to the invention as well as their use as dental material and in particular for the preparation of dental restorations.

BACKGROUND

Glass ceramics are used in dentistry because of their good mechanical and optical properties in particular for the production of dental crowns and small bridges.

It is known from W. Buchalla, “Comparative Fluorescence Spectroscopy Shows Differences in Non-Cavitated Enamel Lesions”, Caries Res. 2005, 39, 150-156 that, under ultraviolet light, natural teeth exhibit a bluish-white fluorescence with wavelengths in the range of from 400 to 650 nm.

Rukmani et al., J. Am. Ceram. Soc. 2007, 90, 706-711, describe the influence of V and Mn colorants on the crystallization behaviour and the optical properties of Ce-doped lithium disilicate glass ceramics. For the production of glass ceramics, a mixture of the starting materials SiO₂, ZrO₂, Li₂CO₃, K₂CO₃, MgCO₃ and Al(PO₃)₃ with CeO₂, V₂O₃ and MnO₂ is produced, the mixture is melted in platinum crucibles at 1500° C., cooled and then subjected to several heat treatments in a tube furnace with an air supply.

EP 0 877 071 A1 and corresponding U.S. Pat. No. 6,010,644, which is hereby incorporated by reference in its entirety, describes glasses and glass ceramics which contain inter alia Eu²⁺ ions and exhibit long-lasting phosphorescence.

DE 10 2009 013 377 A1 describes the use of a borosilicate glass which is doped with CeO₂ or at least one oxide of another lanthanoid, inter alia Eu₂O₃, for increasing antiforgery security of a package by emission of electromagnetic radiation in the range between 300 and 700 nm when irradiated with UV light.

WO 2015/173230 A1 and corresponding U.S. Pat. No. 10,131,569, which is hereby incorporated by reference in its entirety, describes a method for the production of a lithium silicate glass or a lithium silicate glass ceramic, in which a melt of a starting glass which contains cerium ions is exposed to reducing conditions. Ce⁴⁺ ions contained in the starting glass are thereby said to be completely or partially reduced to Ce³⁺ ions which, because of 5d→4f transitions, exhibit a fluorescence in the wavelength range from 320 to 500 nm. A corresponding process for the production of a glass ceramic with SiO₂ as main crystal phase or of a glass which contains nuclei for the crystallization of SiO₂, is known from WO 2017/080853 A1 and corresponding U.S. Pat. No. 10,414,688, which is hereby incorporated by reference in its entirety.

However, it has been shown that the glasses and glass ceramics known from the state of the art have unsatisfactory fluorescence properties and, in particular under UV light, cannot adequately imitate the fluorescence properties of natural tooth material. In particular, the known materials do not exhibit the required fluorescence at all the relevant wavelengths in the UV range. Dental restorations produced from such glass ceramics are thereby recognizable as restorations, in particular under the influence of UV light, or are perceived as missing teeth or defects. Moreover, in the case of the glasses and glass ceramics produced in this way, considerable impairment of the fluorescence properties results through heat treatments under oxidizing conditions, for example during sintering.

SUMMARY

The object of the invention is to provide glass ceramics and glasses which, at excitation wavelengths throughout the entire relevant UV range, above all in the range of from 250 nm to 430 nm and in particular in the range of from 360 nm to 430 nm, exhibit fluorescence and are thus suitable in particular for the production of dental restorations which not only have good mechanical properties, but can also largely imitate the fluorescence properties of natural tooth material at excitation wavelengths throughout the entire relevant UV range. In particular, the glass ceramics and glasses should also be suitable as blending components for setting the fluorescence properties of other glasses and glass ceramics.

DETAILED DESCRIPTION

This object is achieved according to the invention by a glass or a glass ceramic with europium content, which comprise the following components:

SiO₂ 30.0 to 75.0 Al₂O₃ 10.0 to 45.0 Europium, calculated as Eu₂O₃ 0.05 to 5.0.

It has surprisingly been shown that the glass according to the invention and the glass ceramic according to the invention exhibit improved fluorescence properties compared with the state of the art at excitation wavelengths in the range of from 250 to 430 nm and in particular also at excitation wavelengths in the range of from 360 to 430 nm and these fluorescence properties are, in addition, largely stable towards heat treatments and oxidizing conditions.

Without being limited to a specific theory, it is assumed that an equilibrium between Eu²⁺ and Eu³⁺ ions is formed in the glasses and glass ceramics according to the invention. Because of 5d→4f transitions, the Eu²⁺ ions exhibit a fluorescence at excitation wavelengths throughout the entire range of from 250 to 430 nm which is particularly suitable for imitating the fluorescence properties of natural tooth material, in particular in the case of excitation in the UV range.

According to the invention, it is preferred that the glass and the glass ceramic comprise 32.0 to 72.0, in particular 35.0 to 65.0 and preferably 38.0 to 50.0 wt.-% SiO₂.

It is further preferred that the glass and the glass ceramic comprise 15.0 to 40.0, in particular 20.0 to 40.0, preferably 25.0 to 40.0 and particularly preferably 30.0 to 40.0 wt.-% Al₂O₃.

The glass and the glass ceramic preferably comprise 0.1 to 4.0, in particular 0.3 to 3.0, preferably 0.5 to 2.0, more preferably 0.6 to 1.0 and particularly preferably 0.65 to 0.85 wt.-% europium, calculated as Eu₂O₃.

It is further preferred that the glass and the glass ceramic comprise 8.0 to 30.0 wt.-%, in particular 12.0 to 29.0, preferably 15.0 to 28.0 and particularly preferably 20.0 to 27.0 wt.-% Me^(II)O, wherein Me^(II)O is selected from MgO, CaO, SrO and/or ZnO. In a preferred embodiment, the glass and the glass ceramic comprise 8.0 to 30.0, in particular 12.0 to 29.0, preferably 15.0 to 28.0 and particularly preferably 20.0 to 27.0 wt.-% CaO and/or SrO.

Glasses and glass ceramics which comprise at least one and preferably all of the following components in the specified amounts are particularly preferred:

Component wt.-% MgO 0 to 13.0, in particular 3.5 to 13.0 CaO 0 to 22.0, in particular 5.0 to 22.0 SrO 0 to 28.0, in particular 9.0 to 28.0 ZnO 0 to 5.0, in particular 4.0 to 5.0.

It is furthermore preferred that the glass and the glass ceramic comprise 0 to 10.0, in particular 0 to 5.0 and preferably 0 to 1.0 wt.-% BaO, and most preferably are substantially free from BaO.

In a preferred embodiment, the glass and the glass ceramic comprise 0 to 2.0, in particular 0.1 to 1.2 and preferably 0.3 to 0.7 wt.-% tin, calculated as SnO.

Preferably, the glass and the glass ceramic further comprise 0 to 5.0, preferably 0.5 to 4.0 and preferably 1.0 to 3.0 wt.-% cerium, calculated as CeO₂.

The glass and the glass ceramic can further comprise alkali metal oxide Me^(I) ₂O in an amount of from 0 to 15.0, in particular 0 to 10.0, preferably 0 to 5.0, particularly preferably 0 to 1.0 and most preferably 0 to 0.5 wt.-%, wherein this Me^(I) ₂O is selected in particular from Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O and is preferably selected from Li₂O, Na₂O and K₂O. Particularly preferably, the glass and the glass ceramic comprise at least one and in particular all of the following alkali metal oxides Me^(I) ₂O in the specified amounts:

Component wt.-% Li₂O 0 to 5.0 Na₂O 0 to 10.0 K₂O 0 to 14.0 Rb₂O 0 to 7.0 Cs₂O 0 to 13.0.

The glass and the glass ceramic can, furthermore, comprise 0 to 10.0, in particular 0 to 4.0 and preferably 0 to 2.5 wt.-% further oxide of trivalent elements Me^(III) ₂O₃. The term “further oxide of trivalent elements Me^(III) ₂O₃” denotes trivalent oxides with the exception of B₂O₃, Al₂O₃, Eu₂O₃ and Ce₂O₃, wherein this Me^(III) ₂O₃ is selected in particular from Y₂O₃, La₂O₃, Ga₂O₃ and/or In₂O₃. Particularly preferably, the glass and the glass ceramic comprise at least one and in particular all of the following further oxides of trivalent elements Me^(III) ₂O₃ in the specified amounts:

Component wt.-% Y₂O₃ 0 to 3.0 La₂O₃ 0 to 2.0 Ga₂O₃ 0 to 2.0 In₂O₃ 0 to 1.0.

It is furthermore preferred that the glass and the glass ceramic comprise 0 to 3.0, in particular 0 to 2.0 and preferably 0 to 1.0 wt.-% B₂O₃, and most preferably are substantially free from B₂O₃.

Furthermore, the glass and the glass ceramic can comprise further oxide of tetravalent elements Me^(IV)O₂ in an amount of 0 to 15.0, in particular 0 to 4.0 and particularly preferably 0 to 2.5 wt.-%. The term “further oxide of tetravalent elements Me^(IV)O₂” denotes tetravalent oxides with the exception of SiO₂, SnO₂, CeO₂ and TiO₂, wherein this Me^(IV)O₂ is selected in particular from ZrO₂ and/or GeO₂. Particularly preferably, the glass and the glass ceramic comprise at least one and in particular all of the following further oxides of tetravalent elements Me^(IV)O₂ in the specified amounts:

Component wt.-% ZrO₂ 0 to 15.0 GeO₂ 0 to 5.0.

It is furthermore preferred that the glass and the glass ceramic comprise 0 to 5.0, in particular 0 to 2.5 and preferably 0 to 1.0 wt.-% TiO₂ and most preferably is substantially free from TiO₂.

Moreover, the glass and the glass ceramic can comprise oxide of pentavalent elements Me^(V) ₂O₅ in an amount of 0 to 6.0 and in particular 0 to 5.0 wt.-%, wherein this Me^(V) ₂O₅ is selected in particular from P₂O₅, V₂O₅, Ta₂O₅ and/or Nb₂O₅. Particularly preferably, the glass and the glass ceramic comprise at least one and in particular all of the following further oxides of pentavalent elements Me^(V) ₂O₅ in the specified amounts:

Component wt.-% P₂O₃ 0 to 6.0 V₂O₃ 0 to 6.0 Ta₂O₃ 0 to 5.0 Nb₂O₅ 0 to 5.0.

In addition, the glass and the glass ceramic can comprise 0 to 6.0 wt.-% oxide of hexavalent elements Me^(VI)O₃, wherein this Me^(VI)O₃ is selected in particular from WO₃ and/or MoO₃. Particularly preferably, the glass and the glass ceramic comprise at least one and in particular all of the following Me^(VI)O₃ oxides in the specified amounts:

Component wt.-% WO₃ 0 to 6.0 MoO₃ 0 to 5.0.

The glass and the glass ceramic can, furthermore, comprise oxides of further f-elements, such as oxides of Pr, Nd, Gd, Tb, Dy, Er and Yb and in particular oxides of Tb and/or Dy.

Furthermore, the glass and the glass ceramic can comprise 0 to 5.0 and in particular 0 to 1.0 wt.-% fluorine.

A glass and a glass ceramic which comprise at least one and preferably all of the following components in the specified amounts are particularly preferred:

Component wt.-% SiO₂ 32.0 to 72.0 Al₂O₃ 15.0 to 40.0 Europium, calculated as Eu₂O₃ 0.1 to 4.0 Cerium, calculated as CeO₂ 0 to 5.0 Tin, calculated as SnO 0 to 2.0 Me^(I) ₂O 0 to 15.0 Me^(II)O 0 to 30.0 me^(III) ₂O₃ 0 to 10.0 Me^(IV)O₂ 0 to 15.0 Me^(V) ₂O₅ 0 to 6.0 Me^(VI)O₃ 0 to 6.0 Fluorine 0 to 5.0,

wherein Me^(I) ₂O, Me^(II)O, Me^(III) ₂O₃, Me^(IV)O₂, Me^(V) ₂O₅ and Me^(VI)O₃ have in particular the meanings specified above.

In a further particularly preferred embodiment, the glass and the glass ceramic comprise at least one and preferably all of the following components in the specified amounts:

Component wt.-% SiO₂ 32.0 to 72.0 Al₂O₃ 15.0 to 40.0 Europium, calculated as Eu₂O₃ 0.1 to 4.0 Cerium, calculated as CeO₂ 0 to 5.0 Tin, calculated as SnO 0 to 2.0 Li₂O 0 to 5.0 Na₂O 0 to 10.0 K₂O 0 to 14.0 Rb₂O 0 to 7.0 Cs₂O 0 to 13.0 MgO 0 to 13.0 CaO 0 to 22.0 SrO 0 to 28.0 ZnO 0 to 5.0 BaO 0 to 10.0 B₂O₃ 0 to 3.0 Y₂O₃ 0 to 3.0 La₂O₃ 0 to 2.0 Ga₂O₃ 0 to 2.0 In₂O₃ 0 to 1.0 ZrO₂ 0 to 15.0 GeO₂ 0 to 5.0 TiO₂ 0 to 5.0 P₂O₃ 0 to 6.0 V₂O₃ 0 to 6.0 Ta₂O₃ 0 to 5.0 Nb₂O₅ 0 to 5.0 WO₃ 0 to 6.0 MoO₃ 0 to 5.0 Dy₂O₃ 0 to 3.0 Tb₄O₇ 0 to 2.0 Fluorine 0 to 1.0.

The glass ceramic according to the invention preferably comprises at least one aluminosilicate as crystal phase and in particular as main crystal phase. In a further preferred embodiment, the glass ceramic according to the invention comprises a calcium aluminosilicate or strontium aluminosilicate or a mixture thereof, preferably a calcium aluminosilicate or strontium aluminosilicate, as crystal phase and in particular as main crystal phase. Without being limited to a specific theory, it is assumed that in the glass ceramics according to the invention Eu²⁺ ions are incorporated into the crystal lattice of the above-named crystal phases, and the fluorescence properties thereof are thereby further improved and stabilized.

The term “main crystal phase” denotes the crystal phase which has the highest proportion by mass of all the crystal phases present in the glass ceramic. The masses of the crystal phases are determined using in particular the Rietveld method. A suitable method for the quantitative analysis of the crystal phases using the Rietveld method is described e.g. in M. Dittmer's doctoral thesis “Gläser and Glaskeramiken im System MgO—Al₂O₃—SiO₂ mit ZrO₂ als Keimbildner” [Glasses and glass ceramics in the MgO—Al₂O₃—SiO₂ system with ZrO₂ as nucleating agent], University of Jena 2011.

It is further preferred that the glass ceramic according to the invention comprises at least 5 wt.-%, in particular at least 10 wt.-% and preferably at least 20 wt.-% aluminosilicate as crystal phase, in particular in the form of calcium aluminosilicate, strontium aluminosilicate or mixtures thereof.

The type and the amount of the crystal phases formed can be controlled in particular by the composition of the starting glass used, as well as the heat treatment which is used for the production of the glass ceramic from the glass. The examples illustrate this by varying the composition and the heat treatment used.

The invention likewise relates to precursors with a corresponding composition from which the glass ceramic according to the invention can be produced by heat treatment. These precursors are a glass with a corresponding composition (also referred to as starting glass) and a glass with a corresponding composition with nuclei. The term “corresponding composition” means that these precursors comprise the same components in the same amounts as the glass ceramic, wherein the components with the exception of fluorine are calculated as oxides, as is customary in the case of glasses and glass ceramics.

The invention likewise relates to a glass according to the invention which comprises nuclei for the crystallization of an aluminosilicate and in particular of calcium aluminosilicate and/or strontium aluminosilicate. Through heat treatment of the glass according to the invention, the glass with nuclei according to the invention can first be produced, which in turn can be converted through further heat treatment into the glass ceramic according to the invention, in particular with an aluminosilicate as crystal phase and preferably as main crystal phase.

The glass according to the invention is produced in particular in such a way that a mixture of suitable starting materials, such as carbonates, oxides, phosphates and fluorides, is melted at temperatures of in particular from 1500 to 1800° C., for 0.5 to 10 h, and the glass melt obtained is introduced in water in order to produce a granulate. This granulate can be pressed, after grinding, to form a blank, a so-called powder compact, or processed to form a powder.

The invention is therefore likewise directed to a process for the preparation of the glass ceramic according to the invention, in which the glass, in particular the glass with nuclei, is subjected to at least one heat treatment at a temperature of from 1000 to 1500° C., preferably 1050 to 1450° C., for a duration of in particular 10 to 720 min and preferably 30 to 120 min.

Thus, in a preferred embodiment, the invention relates to a process for the preparation of the glass ceramic according to the invention, in which

-   -   (a) powder of the glass according to the invention, optionally         after the addition of further components, such as other glasses,         glass ceramics and/or pressing agents, is pressed to form a         powder compact, and     -   (b) the powder compact is subjected to a heat treatment at a         temperature of from 1000 to 1500° C., preferably 1050 to 1450°         C., for a duration of in particular from 10 to 720 min,         preferably 30 to 120 min.

A nucleation can optionally be carried out before the heat treatment in step (b).

The melt of the starting glass can optionally be reacted with at least one reducing agent. In principle, all the agents which are able to reduce Eu³⁺ ions to Eu²⁺ ions under the conditions of the process come into consideration as reducing agents. Those reducing agents are preferred which can be removed from the glass melt residue-free after the reduction.

In particular, gaseous reducing agents, as well as reducing agents which, after the reduction, are burnt out from the glass melt under the conditions of the process according to the invention, are preferred. Examples of gaseous reducing agents are gases which comprise hydrogen and preferably mixtures of hydrogen and nitrogen. Furthermore, examples of reducing agents are substances which comprise at least one oxidizable carbon atom, in particular carbon, for example graphite, organic salts, carbohydrates and cereal flours.

According to a preferred embodiment, the melt of the starting glass is formed from a glass-forming composition which comprises at least one reducing agent. As the at least one reducing agent, a compound is preferred, which comprises at least one oxidizable carbon atom and is preferably selected from the group consisting of organic salts, carbohydrates and cereal flours. Acetates are examples of particularly suitable organic salts.

In a particularly preferred embodiment, a europium acetate, in particular europium(III) acetate hydrate, is used as reducing agent.

According to a further preferred embodiment, the at least one reducing agent is a reducing gas, wherein the gas preferably comprises hydrogen and preferably comprises hydrogen and nitrogen. Mixtures of hydrogen and nitrogen which comprise about 5 vol.-% hydrogen and are also referred to as forming gas are particularly suitable. The extent of the reduction can be controlled via the amount of the gas supplied and in particular via the flow rate and duration of the gas supply. Preferably, the amount of the effective component of the reducing gas, preferably hydrogen, is 0.05 to 5 l/min, in particular 0.1 to 1 l/min and preferably 0.2 to 0.5 l/min, for a duration of 10 to 180 min, in particular 20 to 120 min and preferably 30 to 90 min.

The invention further relates to a glass according to the invention and a glass ceramic according to the invention, which have a whitish-blue fluorescence in the CIE colour space.

The glasses and glass ceramics with europium content according to the invention are, in particular, suitable as blending components for adjusting the fluorescence properties of other glasses and glass ceramics. A glass or a glass ceramic comprising the glass with europium content according to the invention or the glass ceramic with europium content according to the invention, therefore represent a further subject of the invention. A glass and a glass ceramic are particularly preferred, which comprise the glass with europium content according to the invention or the glass ceramic with europium content according to the invention in an amount of from 0.1 to 50 wt.-%, in particular 0.2 to 40 wt.-%, preferably 0.5 to 30 wt.-%, particularly preferably 1 to 20 wt.-% and more preferably 5 to 10 wt.-%.

The glass with europium content according to the invention or the glass ceramic with europium content according to the invention can in particular be used as component of an inorganic-inorganic composite or in combination with a variety of other glasses and/or glass ceramics, wherein the composites or combinations can in particular be used as dental materials. Particularly preferably, the composites or combinations can be present in the form of sintered blanks. Examples of other glasses and glass ceramics for the production of inorganic-inorganic composites and of combinations are disclosed in DE 43 14 817 A1, DE 44 23 793 C1, DE 44 23 794 C1, DE 44 28 839 A1, DE 196 47 739 A1, DE 197 25 552 A1, DE 100 31 431 A1, EP 0 827 941 A1, EP 0 916 625 A1, WO 00/34196 A2, EP 1 505 041 A1, EP 1 688 398 A1, EP 2 287 122 A1, EP 2 377 831 A1, EP 2 407 439 A1, WO 2013/053863 A2, WO 2013/053864 A2, WO 2013/053865 A2, WO 2013/053866 A2, WO 2013/053867 A2, WO 2013/053868 A2, WO 2013/164256 A1, WO 2014/170168 A1, WO 2014/170170 A2, WO 2015/067643 A1, WO 2015/155038 A1, WO 2015/173394 A1, WO 2016/120146 A1, WO 2017/032745 A1 WO 2017/055010 A1 U.S. Pat. No. 10,457,589, US 2018244563, U.S. Pat. No. 8,759,237, US 2011256409, U.S. Pat. No. 10,501,366, which US patents and published applications are hereby incorporated by reference in their entirety. These glasses and glass ceramics belong to the silicate, borate, phosphate or aluminosilicate group. Preferred glasses and glass ceramics are of the SiO₂—Al₂O₃—K₂O type (with cubic or tetragonal leucite crystals), SiO₂—B₂O₃—Na₂O type, alkali-silicate type, alkali-zinc-silicate type, silico-phosphate type and/or SiO₂—ZrO₂ type. Particularly preferred are lithium-silicate glass ceramics and in particular glass ceramics which comprise lithium metasilicate or lithium disilicate as main crystal phase and optionally further crystal phases such as apatite, diopside, quartz and/or wollastonite, as well as glass ceramics which comprise SiO₂, in particular in the form of low quartz, as main crystal phase. By mixing such glasses or glass ceramics with the glasses and/or glass ceramics with europium content according to the invention, the fluorescence properties can in particular be set as desired.

The glass ceramics according to the invention and the glasses according to the invention, in particular in the form of composites and combinations, are present in particular in the form of powders, granulates or blanks in any shape and size, e.g. monolithic blanks, such as platelets, cuboids or cylinders, or powder compacts, in unsintered, partially sintered or densely sintered form. In these forms, they can easily be further processed, e.g. to form dental restorations. However, they can also be present in the form of dental restorations such as inlays, onlays, crowns, partial crowns, bridges, veneers, facets or abutments.

Dental restorations, such as inlays, onlays, crowns, partial crowns, bridges, veneers, facets or abutments, can be produced from the glass ceramics according to the invention and the glasses according to the invention, in particular in the form of composites and combinations. The invention therefore relates to the use thereof as dental material and in particular the use thereof for the preparation of dental restorations. It is preferred that the glass ceramic or the glass is given the shape of the desired dental restoration by pressing or machining.

The pressing is usually effected under increased pressure and at increased temperature. It is preferred that the pressing is effected at a temperature of from 700 to 1150° C. and in particular 700 to 1000° C. It is further preferred to carry out the pressing at a pressure of from 10 to 30 bar. During pressing, the desired shape change is achieved by viscous flow of the material used. The glass according to the invention and the glass with nuclei according to the invention as well as preferably the glass ceramic according to the invention can be used for the pressing. The glasses and glass ceramics according to the invention can be used in particular in the form of blanks in any shape and size, e.g. monolithic blanks or powder compacts, e.g. in unsintered, partially sintered or densely sintered form.

The machining is usually effected by material-removal processes and in particular by milling and/or grinding. It is particularly preferred that the machining is carried out as part of a CAD/CAM process. The glass according to the invention, the glass with nuclei according to the invention as well as the glass ceramic according to the invention can be used for the machining. The glasses and glass ceramics according to the invention can be used in particular in the form of blanks, e.g. monolithic blanks or powder compacts, e.g. in unsintered, partially sintered or densely sintered form. The glass ceramic according to the invention is preferably used for the machining. The glass ceramic according to the invention can also be used in a not fully crystallized form, which has been produced by heat treatment at a lower temperature. This offers the advantage that an easier machining and thus the use of simpler apparatus for the machining are possible. After the machining of such a partially crystallized material, the latter is regularly subjected to a further heat treatment in order to bring about further crystallization.

The glass ceramics according to the invention and the glasses according to the invention, in particular in the form of composites and combinations, are however also suitable as coating material for e.g. ceramics, glass ceramics and metals. The invention is therefore likewise directed towards the use of the glasses according to the invention or the glass ceramics according to the invention for coating in particular ceramics, glass ceramics and metals.

The invention also relates to a process for coating ceramics, glass ceramics and metals, in which glass ceramic according to the invention or glass according to the invention, in particular in the form of composites and combinations, is applied to the ceramic, the glass ceramic or the metal and exposed to a temperature of at least 600° C.

This can be effected in particular by sintering-on and preferably by pressing-on. In the case of sintering-on, the glass ceramic or the glass is applied in the usual way, e.g. as powder, to the material to be coated, such as ceramic, glass ceramic or metal, and then sintered. In the case of the preferred pressing-on, glass ceramic according to the invention or glass according to the invention is pressed on, e.g. in the form of powder compacts or monolithic blanks, at an increased temperature of e.g. from 700 to 1150° C. and in particular 700 to 1000° C., and with application of pressure, e.g. from 10 to 30 bar. For this, the methods described in EP 231 773 and the press furnace disclosed there can in particular be used. Suitable commercial furnaces are the Programat-type furnaces from Ivoclar Vivadent AG, Liechtenstein.

Because of the above-described properties of the glass ceramics according to the invention and the glasses according to the invention, these are suitable in particular for use in dentistry. A subject of the invention is therefore also the use of the glass ceramics according to the invention or the glasses according to the invention, in particular in the form of composites and combinations, as dental material and in particular for the preparation of dental restorations or as coating material for dental restorations, such as crowns, bridges and abutments.

The invention therefore also relates to a process for the preparation of a dental restoration, in particular an inlay, onlay, crown, partial crown, bridge, veneer, facet or abutment, in which the glass ceramic according to the invention or the glass according to the invention, in particular in the form of composites and combinations, is given the shape of the desired dental restoration by pressing, sintering or machining, in particular in a CAD/CAM process.

The invention is described in further detail in the following with reference to non-limitative examples.

EXAMPLES

A total of 21 glasses according to the invention were produced with the compositions specified in Table I, wherein the oxidation states of the specified oxides relate to the oxidation states of the raw materials used. The glasses were crystallized to form glass ceramics according to Table II. Herein,

T_(g) denotes glass transition temperature, determined by means of DSC T_(s) and t_(s) denote temperature and time used for melting T_(Sinter) and t_(sinter) denote temperature and time used for sintering.

In addition, the glasses or glass ceramics according to Table III were mixed with further glasses and sintered to form glass ceramic bodies.

A) Preparation of Glasses According to the Invention

In the examples, starting glasses with the compositions specified in Table I were first melted on a scale of from 100 to 200 g from usual raw materials at the temperature T_(s) for a duration t_(s). Glass frits were produced by pouring the molten starting glasses into water. The fluorescence properties of the glass frits thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm were determined visually by means of a UV lamp and are reproduced in Table II. According to this, all the glasses obtained in the examples exhibited a fluorescence, in particular at excitation wavelengths of 366, 395 and 430 nm.

The three method variants B) to D) specified below were used for the further processing of the glass frits:

B) Preparation of Glass Ceramics According to the Invention

In Examples 1 to 13, the glass frits obtained were ground to a grain size of <45 μm in a zirconium oxide mill. About 4 g of these powders were then pressed to form cylindrical blanks and, according to Table II, sintered at a temperature T_(sinter) and for a holding time of t_(sinter) to form dense glass ceramic bodies, wherein this was effected for sintering temperatures of up to 1200° C. in a vacuum in a Programat®-type sintering furnace (Ivoclar Vivadent AG), and for sintering temperatures above 1200° C. in a normal atmosphere in an LHT 02/16-type sintering furnace (Nabertherm). The fluorescence properties of the glass ceramics thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm, respectively, were determined visually by means of a UV lamp and are reproduced in Table II. According to this, the glass ceramics obtained exhibited a fluorescence, in particular at excitation wavelengths of 366, 395 and 430 nm.

C) Glasses According to the Invention as Blending Components

The glass frits obtained in Examples 14 to 21 were comminuted and sieved to a grain size of <25 μm. The glass powders obtained were added to pulverized lithium silicate glasses according to Table III. In each case about 4 g of these mixtures were then pressed to form cylindrical or disc-shaped blanks and sintered in a sintering furnace (Programat® from Ivoclar Vivadent AG) to form dense glass ceramic bodies. The fluorescence properties of the glass ceramic bodies thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm, respectively, were determined visually by means of a UV lamp and are reproduced in Table III. According to this, all the glass ceramic bodies obtained exhibited a fluorescence, in particular at excitation wavelengths of 366, 395 and 430 nm.

D) Glass Ceramics According to the Invention as Blending Components

The glass ceramics obtained in Examples 1, 2, 4 and 9 and the glass ceramic obtained after sintering at 1110° C. in Example 5 were comminuted and sieved to a grain size of <25 μm. The glass ceramic powders obtained were added to pulverized lithium silicate glasses according to Table III. In each case about 4 g of these mixtures were then pressed to form cylindrical or disc-shaped blanks or to form pressed stubs and sintered in a sintering furnace (Programat® from Ivoclar Vivadent AG) or hot-pressed to form dense glass ceramic bodies. The fluorescence properties of the glass ceramic bodies thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm, respectively, were determined visually by means of a UV lamp and are reproduced in Table III. According to this, all the glass ceramic bodies obtained exhibited a fluorescence, in particular at excitation wavelengths of 366 nm. As crystal phases, calcium aluminosilicates such as anorthite were obtained in CaO-containing compositions, and strontium aluminosilicates such as slawsonite were obtained in SrO-containing compositions.

TABLE I Example 1 2 3 4 5 6 7 8 9 10 11 Composition wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% SiO₂ 45.0 39.5 44.8 38.9 39.6 39.7 46.0 46.8 37.9 39.9 44.1 Al₂O₃ 37.3 32.7 37.1 32.3 33.0 33.0 34.3 31.0 31.4 33.1 36.7 Eu₂O₃  0.7  0.7  0.7  0.7  0.7 —  0.8  0.8  2.5  0.1  0.7 Eu₂O₃* — — — — —  0.6 — — — — — MgO — — — — — — — — — — — CaO 16.4 — 16.3 — — — 18.9 21.4 — — 16.1 SrO — 26.6 — 26.2 26.7 26.7 — — 25.5 26.9 — ZnO — — — — — — — — — — — SnO  0.6  0.5  1.1  0.5 — — — — — — — Li₂O — — — — — — — — — — — Na₂O — — — — — — — — — — — K₂O — — — — — — — — — — — CeO₂ — — — — — — — — — —  2.4 ZrO₂ — — — — — — — — — — — Dy₂O₃ — — — — — — — —  2.7 — — Tb₄O₇ — — —  1.4 — — — — — — — Σ 100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  Example 12 13 14 15 16 17 18 19 20 21** Composition wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% SiO₂ 39.4 38.9 47.3 40.5 67.8 64.3 61.4 63.9 47.5 47.5 Al₂O₃ 32.7 32.3 39.2 33.6 26.0 24.7 23.5 18.3 39.3 39.3 Eu₂O₃  1.3  2.6  0.8  0.7  0.8  0.8  0.7  0.8  0.8  0.8 Eu₂O₃* — — — — — — — — — — MgO — — 12.4 10.6 — — —  4.5 12.4 12.4 CaO — — — — — — — — — — SrO 26.6 26.2 — — — — — — — — ZnO — — — — — — —  4.5 — — SnO — —  0.3  0.6  0.6  0.6  0.6  0.6 — — Li₂O — — — —  4.8 — — — — — Na₂O — — — — —  9.6 — — — — K₂O — — — — — — 13.8 — — — CeO₂ — — — — — — — — — — ZrO₂ — — — 14.0 — — —  7.4 — — Dy₂O₃ — — — — — — — — — — Tb₄O₇ — — — — — — — — — — Σ 100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  *Used as europium(III) acetate hydrate **Starting mixture for the glass melt contained 10 wt.-% sugar

TABLE II Example 1 2 3 4 5 6 T_(g) [° C.]  848  881  847  860  878  875 T_(s) [° C.] 1600 1600 1650 1680 1650 1650 t_(s) [min]  60  60  60  60  60  60 Fluorescence blue-white yellowish- blue-white white light light pink glass 254 nm* white blue-white Fluorescence blue-white yellowish blue-white strong blue-white blue-white glass 366 nm* white white Fluorescence blue-white yellowish blue-white white blue-white yellowish glass 395 nm* white white Fluorescence yellowish- yellowish blue-white white yellowish- yellowish- glass 430 nm* white white yellow yellow T_(Sinter) [° C.] 1140 1360 1500 1130 1360 1110 1360 1360 t_(Sinter) [min]  60  60  60  60  60  60  60  60 Fluorescence pale pale pale blue-white pale pale pale glass ceramic blue-white blue-white blue-white blue-white blue-white blue-white 254 nm* Fluorescence blue-white strong strong white strong strong strong glass ceramic blue-white blue-white blue-white blue-white blue-white 366 nm* Fluorescence blue-white white blue-white blue-white blue-white blue-white blue-white glass ceramic 395 nm* Fluorescence blue-white white white blue-white blue-white blue-white glass ceramic 430 nm* Crystal CAS SLA phase(s)** Example 7 8 9 10 11 12 13 T_(g) [° C.]  846  833  860  871  852  847  867 T_(s) [° C ] 1600 1600 1650 1650 + 1680 1600 1650 1650 t_(s) [min]  60  60  60 45 + 15  60  60  60 Fluorescence light pink orange blue-white white light orange glass 254 nm* pink pink Fluorescence blue-white blue-white yellow blue-white blue-white blue-white yellowish glass 366 nm* Fluorescence yellowish yellowish orange blue-white light yellowish yellow- glass 395 nm* white white orange to orange to pink greenish Fluorescence light light orange blue-white light yellowish yellow- glass 430 nm* yellowish yellow orange to orange to pink greenish T_(Sinter) [° C.] 1080 1150 1360 1360 1120 1400 1360 t_(Sinter) [min]  60  60  60  60  60  720  60 Fluorescence strong blue-white blue-white blue-white pale blue glass ceramic pink blue-white 254 nm* Fluorescence strong strong blue-white blue-white blue-white strong strong glass ceramic blue-white blue-white blue-white blue 366 nm* Fluorescence blue-white blue-white blue-white blue-white pale pink blue-white blue glass ceramic to to pink 395 nm* pink Fluorescence pale pale pink blue-white blue-white pink white blue glass ceramic white 430 nm* Crystal AOT, CAS AOT, CAS, SLA, MLT phase(s)** WLT Example 14 15 16 17 18 19 20 21 T_(g) [° C.]  783 751 T_(s) [° C.] 1600 1650 1600 + 1650 + 1650 + 1690 1690 1650 + 1690 1600 1600 1670 t_(s) [min]  60  60 60 + 60 + 15 60 + 40 60 45 + 60 60 15 Fluorescence blue-white blue-white blue-white blue-white blue-white blue-white blue-white strong glass 254 nm* blue-white Fluorescence blue-white blue-white blue-white blue-white blue-white blue-white blue-white strong glass 366 nm* blue-white Fluorescence blue-white yellowish blue-white blue-white blue-white yellowish blue-white strong glass 395 nm* white white blue-white Fluorescence blue-white yellowish blue-white blue-white blue-white yellowish blue-white strong glass 430 nm* white white blue-white *Fluorescence of the glass or of the glass ceramic at the specified excitation wavelength **AOT: Anorthite (calcium aluminosilicate); CAS: calcium aluminosilicate; MLT: mullite (aluminium silicate); SLA: slawsonite (strontium calcium aluminosilicate); WLT: wollastonite (calcium silicate)

TABLE III Fluores- Fluores- Fluores- Fluores- Heat cence cence cence cence Component A % A** Component B % B** treatment 254 nm* 366 nm* 395 nm* 430 nm* Glass 10 Glass according to 90 Sintering blue-white pale pale according to Example 10 of 790° C./10 min white white Example 14 WO2016/120146A1 (cylinder) Glass 10 Glass according to 90 Sintering blue-white white pale according to Example 31 of 820° C./10 min white Example 14 WO2017/055010A1 (cylinder) Glass 30 Glass according to 70 Sintering blue-white pale pale according to Example 31 of 800° C./10 min white white Example 14 WO2017/055010A1 (cylinder) Glass 10 Glass according to 90 Sintering green- pale pale according to Example 3 of 880° C./10 min yellow white white Example 21 EP2377831A1 (cylinder) Glass 10 Glass according to 90 Sintering yellow- white pale according to Example 3 of 900° C./10 min white white Example 21 EP2377831A1 (disc) Glass 20 Glass according to 80 Sintering pale pale light according to Example 3 of 900° C./10 min yellow- yellow- yellow Example 21 EP2377831A1 (cylinder) white white Glass ceramic 1 Glass according to 99 Sintering blue-white according to Example 9 of 940° C./10 min Example 1 EP1688398A1 (disc) Glass ceramic 5 Glass according to 95 Sintering light according to Example 9 of 940° C./10 min blue-white Example 1 EP1688398A1 (disc) Glass ceramic 5 Glass according to 95 Sintering blue-white blue-white according to Example 31 of 900° C./10 min Example 1 WO2017/055010A1 (disc) Glass ceramic 5 Glass according to 95 Sintering light blue-white blue-white pale according to WO2017/032745A1 830° C./60 min white blue-white Example 1 (cylinder) Glass ceramic 1 Glass according to 99 Sintering blue-white pale according to WO2017/032745A1 820° C./60 min blue-white Example 2 (disc) Glass ceramic 5 Glass according to 95 Sintering pale strong blue-white light according to WO2017/032745A1 820° C./60 min blue-white blue-white blue-white Example 2 (disc) Glass ceramic 5 Glass according to 95 Hot pressing strong pale according to Example 3 of 920° C./25 min blue-white blue-white Example 2 EP2377831A1 (pressed stub) Glass ceramic 5 Glass according to 95 Sintering light strong pale pale according to Example 3 of 900° C./10 min white blue-white blue-white blue-white Example 2 EP2377831A1 (disc) Glass ceramic 10 Glass according to 90 Sintering light strong blue-white pale according to Example 3 of 900° C./10 min white blue-white blue-white Example 2 EP2377831A1 (disc) Glass ceramic 10 Glass according to 90 Sintering blue-white strong blue-white white according to Example 3 of 890° C./10 min blue-white Example 2 EP2377831A1 (cylinder) Glass ceramic 5 Glass according to 95 Sintering pale blue strong white white according to Example 3 of 890° C./10 min blue Example 5 EP2377831A1 (cylinder) Glass ceramic 5 Glass according to 95 Sintering pale blue strong blue-white pale blue according to Example 3 of 900° C./25 min blue-white Example 5 EP2377831A1 (cylinder) Glass ceramic 10 Glass according to 90 Sintering pale blue strong blue-white light according to Example 3 of 900° C./10 min blue-white white Example 5 EP2377831A1 (cylinder) Glass ceramic 10 Glass according to 90 Hot pressing pale blue strong blue-white pale according to Example 3 of 920° C./25 min blue-white white Example 5 EP2377831A1 (pressed stub) Glass ceramic 10 Glass according to 90 Sintering blue-white strong blue-white blue-white according to WO2017/032745A1 810° C./30 min blue-white Example 4 (disc) Glass ceramic 10 Glass according to 90 Sintering blue-white strong blue-white blue-white according to WO2017/032745A1 810° C./30 min blue-white Example 9 (disc) *Fluorescence of the heat-treated body at the specified excitation wavelength; **wt.-% 

1. Glass or glass ceramic with europium content, which comprise the following components: Component wt.-% SiO₂ 30.0 to 75.0 Al₂O₃ 10.0 to 45.0 Europium, calculated as Eu₂O₃ 0.05 to 5.0.


2. Glass or glass ceramic according to claim 1, which comprise 32.0 to 72.0 wt.-% SiO₂.
 3. Glass or glass ceramic according to claim 1, which comprise 15.0 to 40.0 wt.-% Al₂O₃.
 4. Glass or glass ceramic according to claim 1, which comprise 0.1 to 4.0 wt.-% europium, calculated as Eu₂O₃.
 5. Glass or glass ceramic according to claim 1, which comprise 8.0 to 30.0 wt.-% Me^(II)O wherein Me^(II)O is selected from MgO, CaO, SrO and/or ZnO.
 6. Glass or glass ceramic according to claim 1, which comprise 8.0 to 30.0 wt.-% CaO and/or SrO.
 7. Glass or glass ceramic according to claim 1, which comprise at least one of the following components in the specified amounts: Component wt.-% MgO 0 to 13.0 CaO 0 to 22.0 SrO 0 to 28.0 ZnO 0 to 5.0.


8. Glass or glass ceramic according to claim 1, which comprise 0 to 10.0 wt.-% BaO.
 9. Glass or glass ceramic according to claim 1, which comprise 0 to 2.0 wt.-% tin, calculated as SnO.
 10. Glass or glass ceramic according to claim 1, which comprise 0 to 5.0 wt.-% cerium, calculated as CeO₂.
 11. Glass or glass ceramic according to claim 1, containing 0 to 3.0 wt.-% B₂O₃.
 12. Glass or glass ceramic according to claim 1, which comprise at least one of the following components in the specified amounts: Component wt.-% SiO₂ 32.0 to 72.0 Al₂O₃ 15.0 to 40.0 Europium, calculated as Eu₂O₃ 0.1 to 4.0 Cerium, calculated as CeO₂ 0 to 5.0 Tin, calculated as SnO 0 to 2.0 Me^(I) ₂O 0 to 15.0 Me^(II)O 0 to 30.0 Me^(III) ₂O₃ 0 to 10.0 Me^(IV)O₂ 0 to 15.0 Me^(V) ₂O₅ 0 to 6.0 Me^(VI)O₃ 0 to 6.0 Fluorine 0 to 5.0,

wherein Me^(I) ₂O is selected from Li₂O, Na₂O, K₂O, Rb₂O and/or Cs₂O, Me^(II)O is selected from MgO, CaO, SrO and/or Zno, Me^(III) ₂O₃ is selected from Y₂O₃, La₂O₃, Ga₂O₃ and/or In₂O₃, Me^(IV)O₂ is selected from ZrO₂ and/or GeO₂, Me^(V) ₂O₅ is selected from P₂O₅, V₂O₅, Ta₂O₅ and/or Nb₂O₅ and Me^(VI)O₃ is selected from WO₃ and/or MoO₃.
 13. Glass ceramic according to claim 1, which comprises at least one aluminosilicate as crystal phase.
 14. Glass ceramic according to claim 1, which comprises at least 5 wt.-% aluminosilicate as crystal phase.
 15. Glass according to claim 1, which comprises nuclei for the crystallization of an aluminosilicate.
 16. Glass or glass ceramic, which comprise the glass or the glass ceramic with europium content according to claim
 1. 17. Glass or glass ceramic according to claim 1, wherein the glass and the glass ceramic are present in the form of a powder, a granulate, a blank or a dental restoration.
 18. Glass or glass ceramic according to claim 1, which exhibit fluorescence at an excitation wavelength in the range of from 250 nm to 430 nm. 